Conductive resin composition and process for producing the same

ABSTRACT

A resin composition comprising a polyamide, a polyphenylene ether, an impact modifier, and a carbon type filler for an electrically conductive use, the filler residing in a phase of the polyphenylene ether. The resin composition of the present invention has excellent electrical conductivity, fluidity, and an excellent balance of a coefficient of linear expansion and an impact resistance, and generation of fines caused by pelletizing thereof can be largely suppressed when processing of an extrusion thereof is conducted.

TECHNICAL FIELD

[0001] The present invention relates to a resin composition which hasexcellent electrical conductivity, fluidity, and an excellent balance ofa coefficient of linear expansion and an impact resistance, and whereingeneration of fines caused by pelletizing is largely suppressed whenprocessing of extrusion thereof is conducted, and to a method forproducing thereof.

[0002] The composition of the present invention can be used in broadfields such as electrical or electronic parts, OA parts, parts ofvehicles, mechanical parts, etc., and among them, it can be suitablyused in exterior automobile parts wherein electrostatic coating ispossible.

BACKGROUND ART

[0003] A polyphenylene ether resin has an excellent mechanical property,electrical property, and thermal resistance, and has an excellentdimensional stability, and therefore it is used in a broad range.However, a processing property of molding thereof by itself is inferior.In order to improve the processing property, the technique offormulating a polyamide therewith is proposed in JP-B-45-997. And eventhereafter, various improvements have been added thereto, and atpresent, it has become a material which has many varied uses.

[0004] Having heightened consciousness to environment of recent years asa background, to improve fuel cost of automobiles, study of utilizing aresin as exterior automobile materials has been conducted.

[0005] Especially, in Europe, a need has arisen for materials which canbe electrostatically coated using the same coating line as that used fora steel plate and thus providing materials with electrical conductivity.

[0006] As a conventional prior art concerning exterior automobilematerials, it is described, for instance, in JP-A-2-163158,JP-A-4-372656, and JP-A-6-306275, that high balance of a coefficient oflinear expansion and an impact resistance is important, and acomposition comprising a polyamide resin, a polyphenylene ether, and aninorganic filler is useful.

[0007] However, in the above-described conventional prior art, since thecoefficient of linear expansion is decreased by adding the inorganicfiller, sufficient level of an impact resistance was not attained, andit has not been afforded to a practical use, which has been the actualstatus.

[0008] From the above-described standpoint, the technique whereinimprovement in balance of a coefficient of linear expansion and animpact resistance can be attained by using a composition substantiallynot containing an inorganic filler is required.

[0009] JP-A-6-287446 discloses a composition comprising a polyamide, apolyphenylene ether, a styrene type resin and a pigment, whereinyellowing of the composition is reduced by dispersing the pigment in aphase of the polyphenylene ether and the styrene type resin.

[0010] However, since the composition obtained by the technique asdescribed in JP-A-6-287446 contains a large amount of a styrene typeresin, a coefficient of linear expansion thereof becomes high and animpact resistance thereof is also largely decreased. Also it has not inthe least electrical conductivity necessary for electrostatic coating,and therefore it can not be used for exterior automobile parts whereinelectrostatic coating is possible.

[0011] To provide a polymer alloy of a polyphenylene ether and apolyamide with electrical conductivity, JP-A-2-201811 discloses atechnique of making a carbon black present mainly in a phase of thepolyamide in a mixture of a polyphenylene ether, a polyamide, and acarbon black.

[0012] However, as in the technique as disclosed in JP-A-2-201811, whena large amount of carbon black is formulated in a phase of a polyamide,the polyamide becomes extremely fragile and highly viscous, andtherefore an impact resistance and fluidity as a composition are greatlyworsened. Also, a coefficient of linear expansion thereof is greatlyworsened. This is thought to be because an orientation and acrystallization of the polyamide has been inhibited under the influenceof an isotropic filler having electrical conductivity.

[0013] Further, in the above-stated conventional prior art, a largeamount of swarf which is called as “fines caused by pelletizing”(hereinafter sometimes referred to as “fines”) is generated in apelletizing step (a step wherein a strand extruded from an extruder iscut to form pellets) on processing. Usually, it is difficult to removethese fines completely.

[0014] These fines caused by pelletizing, in a place of fabrication,attach to a pellet drier, a pneumatic transportation lines of a moldingmachine, a hopper part of a molding machine, etc., which necessitatescleaning upon a change of resin type causing greatly decreasedproductivity. Therefore, this matter as well as the performance of theabove arts has been an item always demanded to be improved.

[0015] As above, in the conventional prior art, a material which hasexcellent electrical conductivity, fluidity, and an excellent balance ofa coefficient of linear expansion and an impact resistance, and whereingeneration of fines caused by pelletizing is greatly suppressed, has notheretofore been available.

[0016] Moreover, exterior automobile materials have many necessaryproperties in addition to the above-described characteristic properties,and for instance, JP-A-60-65035 describes that high adhesion propertieswith a coating are also required.

[0017] The present invention aims to solve the problems which have notbeen solved by the above stated prior art.

[0018] It is therefore an object of the present invention to provide aresin composition which has excellent electrical conductivity, fluidity,and an excellent balance of a coefficient of linear expansion and animpact resistance, and wherein generation of fines caused by pelletizingis largely suppressed.

DISCLOSURE OF THE INVENTION

[0019] The present inventors have intensively studied to solve theproblem as described above, and as a result, surprisingly, they havefound that, by making a carbon type filler for an electricallyconductive use reside in a phase of a polyphenylene ether, a resincomposition which has excellent electrical conductivity, fluidity, andan excellent balance of a coefficient of linear expansion and an impactresistance, and wherein generation of fines caused by pelletizing islargely suppressed, can be obtained. Thus, the present invention hasbeen accomplished.

[0020] The resin composition of the present invention comprises apolyamide, a polyphenylene ether, an impact modifier, and a carbon typefiller for an electrically conductive use, the carbon type fillerresiding in a phase of the polyphenylene ether.

[0021] The present invention also relates to a process for producing theabove-described resin composition, wherein the carbon type filler for anelectrically conductive use is preliminarily melted and kneaded with animpact modifier.

BRIEF DESCRIPTION OF THE DRAWINGS

[0022]FIG. 1 is a drawing of seeing through a transmission electronmicroscope a super sliced piece of pellets of Example 1.

[0023]FIG. 2 is a schematic drawing of an electron microscope in FIG. 1.

[0024]FIG. 3 is a drawing of seeing through a transmission electronmicroscope a super sliced piece of pellets of Comparative Example 1.

[0025]FIG. 4 is a schematic drawing of an electron microscope in FIG. 3.

BEST MODE TO CARRY OUT THE INVENTION

[0026] Hereinafter, the present invention is explained in detail.

[0027] A type of a polyamide which can be used in the present inventionis any one which has an amido bond {—NH—C(═O)—} in the main chain of thepolymer.

[0028] Generally, a polyamide can be obtained by a ring openingpolymerization of lactams, a condensation polymerization of a diamineand a dicarboxylic acid, and a condensation polymerization of anaminocarboxylic acid, etc., but is not limited thereto.

[0029] As the above-described diamine, an aliphatic, an alicyclic, andan aromatic diamine are exemplified, and specifically, tetramethylenediamine, hexamethylene diamine, undecamethylene diamine, dodecamethylenediamine, tridecamethylene diamine, 2,2,4-trimethylhexamethylene diamine,2,4,4-trimethylhexamethylene diamine, 5-methylnanomethylene diamine,1,3-bisaminomethyl cyclohexane, 1,4-bisaminomethyl cyclohexane,m-phenylene diamine, p-phenylene diamine, m-xylylene diamine, andp-xylylene diamine, are mentioned.

[0030] As the dicarboxylic acid, an aliphatic, an alicyclic, and anaromatic dicarboxylic acid are exemplified, and specifically, adipicacid, suberic acid, azelaic acid, sebacic acid, dodecanoic diacid,1,1,3-tridecanoic diacid, 1,3-cyclohexane dicarboxylic acid,terephthalic acid, isophthalic acid, naphthalene dicarboxylic acid,dimmer acid, etc., are mentioned.

[0031] As the lactams, specifically, ε-caprolactam, enanthlactam,ω-laurocaprolactam, etc., are mentioned.

[0032] Further, as the aminocarboxylic acid, specifically,ε-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid,9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid,13-aminotridecanoic acid, etc., are mentioned.

[0033] In the present invention, any of copolymer polyamides can beused, which is obtained by conducting a condensation polymerizationsingly of or in a mixture of at least two sorts of the above lactams,diamines, dicarboxylic acids and aminocarboxylic acids.

[0034] Moreover, polyamides obtained by polymerizing the above lactams,diamines, dicarboxylic acids and aminocarboxylic acids in a reactor forthe polymerization to a stage of an oligomer having a low molecularweight, and further polymerizing to a stage thereof having a highmolecular weight with such as an extruder, can suitably be used.

[0035] As a polyamide especially usefully employed in the presentinvention, a polyamide 6, a polyamide 6,6, a polyamide 4,6, a polyamide11, a polyamide 12, a polyamide 6,10, a polyamide 6,12, a polyamide6/6,6, a polyamide 6/6,12, a polyamide MXD, 6 (MXD: m-xylylene diamine),a polyamide 6/MXD, 6, a polyamide 6,6/MXD, 6, a polyamide 6,T, apolyamide 6,I, a polyamide 6/6,T, a polyamide 6/6,I, a polyamide6,6/6,T, a polyamide 6,6/6,I, a polyamide 6/6,T/6,I, a polyamide6,6/6,T/6,I, a polyamide 6/12/6,T, a polyamide 6,6/12/6,T, a polyamide6/12/6,I, a polyamide 6,6/12/6,I, etc., are exemplified, and polyamidesobtained by copolymerizing plural of polyamides with an extruder or thelike can also be usable.

[0036] These may surely be used in a combination of at least two sortsthereof.

[0037] A preferable number average molecular weight of a polyamide usedin the present invention is 5,000 to 100,000, preferably 7,000 to30,000, more preferably 9,000 to 15,000.

[0038] The polyamide in the present invention may be a mixture ofseveral polyamides having different molecular weights. For instance, amixture of a low molecular weight polyamide having a number averagemolecular weight of not higher than 10,000, and a high molecular weightpolyamide having a molecular weight of not lower than 30,000, and amixture of a low molecular weight polyamide having a number averagemolecular weight of not higher than 10,000, and a general polyamidehaving a molecular weight to the extent of 15,000, are exemplified, butare not limited thereto.

[0039] These may surely be used in a mixture of different kinds ofpolyamides which have different molecular weights.

[0040] A terminal group of a polyamide has an effect on a reaction witha polyphenylene ether. A polyamide has generally an amino group and acarboxyl group as terminal groups thereof. Generally, in an alloy of apolyamide and a polyphenylene ether type, when the concentration of acarboxyl group is higher than the concentration of an amino group, animpact resistance thereof is decreased and fluidity thereof is improved,whereas when the concentration of an amino group is higher than theconcentration of a carboxyl group, an impact resistance thereof isimproved and fluidity thereof is decreased,

[0041] A preferable ratio of amino groups/carboxyl groups is 9/1 to 1/9,more preferably 8/2 to 1/9, further preferably 6/4 to 1/9.

[0042] The concentration of terminal amino groups is preferably at least10 milliequivalent/kg, more preferably at least 30 milliequivalent/kg.

[0043] As a method for adjusting a terminal group of these polyamides, amethod known to a person skilled in the art may be used. For instance,addition of diamines and dicarboxylic acids, and addition of amonocarboxylic acid, on polymerization of a polyamide, are mentioned.

[0044] The polyamide in the present invention may surely be a mixture ofplural polyamides having different concentrations of a terminal groupthereof.

[0045] Further, known additives which may be added to a polyamide, maybe present in concentrations of less than 10 parts by weight based on100 parts by weight of a polyamide.

[0046] The polyphenylene ether which can be used in the presentinvention is a homopolymer or a copolymer or both composed of thestructural unit represented by the formula as shown below,

[0047] wherein R₁ and R₄ independently represent hydrogen, halogen,primary or secondary lower alkyl, phenyl, haloalkyl, aminoalkyl,hydrocarbonoxy, or halohydrocarbonoxy, with a proviso that at least twocarbon atoms are between a halogen atom and an oxygen atom, and R₂ andR₃ independently represent hydrogen, halogen, primary or secondary loweralkyl, phenyl, haloalkyl, hydrocarbonoxy, or halohydrocarbonoxy, with aproviso that at least two carbon atoms separate a halogen atom and anoxygen atom.

[0048] As a specific example of the polyphenylene ether according to thepresent invention, for instance, poly(2,6-dimethyl-1,4-phenylene ether),poly(2-methyl-6-ethyl-1,4-phenylene ether),poly(2-methyl-6-phenyl-1,4-phenylene ether),poly(2,6-dichloro-1,4-phenylene ether), etc., are exemplified, andfurther a copolymer of a polyphenylene ether such as a copolymer of2,6-dimethylphenol with other phenols (for example,2,3,6-trimethylphenol, and 2-methyl-6-butylphenol), is exemplified.Among these, poly(2,6-dimethyl-1,4-phenylene ether), and a copolymer of2,6-dimethylphenol with 2,3,6-trimethylphenol are preferred, andpoly(2,6-dimethyl-1,4-phenylene ether) is most preferred.

[0049] Any known method can be employed for producing polyphenyleneethers useful in the present invention. One such example is described inU.S. Pat. No. 3,306,874, wherein suitable polyethylene ethers are easilyproduced by employing a complex of copper (I) chloride and an amine as acatalyst, and conducting an oxidative polymerization of, for example,2,6-dimethylphenol. Besides this, polyphenylene ethers can be easilyproduced by methods as described in U.S. Pat. Nos. 3,306,875, 3,257,357,and 3,257,358; and JP-B-52-17880, JP-A-50-51197, JP-A-63-152628, etc.

[0050] A reduced viscosity of a polyphenylene ether as can be used inthe present invention (0.5 g/dl, in a solution of chloroform, measuredat 30° C.) is preferably in the range of 0.15 to 0.70 dl/g, morepreferably in the range of 0.20 to 0.60 dl/g, most preferably in therange of 0.40 to 0.55 dl/g.

[0051] Even a blend of at least two sorts of polyphenylene ethers havingdifferent reduced viscosities can be used without any problem. Forinstance, a mixture of a polyphenylene ether having a reduced viscosityof not higher than 0.45 dl/g and a polyphenylene ether having a reducedviscosity of not lower than 0.50 dl/g, a mixture of a low molecularweight polyphenylene ether having a reduced viscosity of not higher than0.40 dl/g and a polyphenylene ether having a reduced viscosity of notlower than 0.50 dl/g, etc., are exemplified, but of course, it is notlimited thereto.

[0052] Concerning a polyphenylene ether used in the present invention,an organic solvent, from the polymerization, may reside therein in anamount of less than 5% by weight based on 100 parts by weight of apolyphenylene ether. It is difficult to completely remove the organicsolvent owing to a solvent for a polymerization at a drying step afterpolymerization, and it usually remains present in the range of severalhundreds ppm to several %. As the organic solvent from thepolymerization as stated herein, at least one of each of isomers oftoluene, and xylene, ethylbenzene, alcohols having a carbon number of 1to 5, chloroform, dichloromethane, chlorobenzene, dichlorobenzene, etc.,are exemplified.

[0053] Further, a polyphenylene ether which can be used in the presentinvention may be a wholly or a partly modified polyphenylene ether.

[0054] The modified polyphenylene ether referred to herein means apolyphenylene ether which has been modified with at least one sort of amodifying compound which has in the molecular structure thereof at leastone C—C double bond or triple bond, and has at least one of a carboxylicacid group, an acid anhydride group, an amino group, a hydroxyl group,or a glycidyl group.

[0055] As a method for producing the modified polyphenylene ether, (1) amethod for reacting a polyphenylene ether with a modifying compound in apresence or absence of a radical initiator, in the range of atemperature of not lower than 100° C. and lower than the glasstransition temperature of the polyphenylene ether, and without meltingthe polyphenylene ether,

[0056] (2) a method for reacting it with a modifying compound by meltingand kneading in the presence or absence of a radical initiator, and inthe range of a temperature of not lower than the glass transitiontemperature of a polyphenylene ether and not higher than 360° C.,

[0057] (3) a method for reacting in a solution a polyphenylene etherwith a modifying compound in the presence or absence of a radicalinitiator, at a temperature of lower than a glass transition temperatureof the polyphenylene ether,

[0058] etc., are exemplified. Any of these methods may be usable, butmethods (1) and (2) are preferable.

[0059] Next, at least one sort of a modifying compound which has, in themolecular structure thereof, at least one C—C double bond or triplebond, and at least one of: a carboxylic acid group, an acid anhydridegroup, an amino group, a hydroxyl group, or a glycidyl group, isspecifically explained.

[0060] As a modifying compound which has in the molecule thereof atleast one C—C double bond, and a carboxylic acid group or an acidanhydride group at the same time, a maleic acid, a fumaric acid, achloromaleic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, an acidanhydride thereof, etc., are exemplified. Especially, a fumaric acid, amaleic acid, and a maleic anhydride are preferred, and a fumaric acid,and a maleic anhydride are particularly preferred.

[0061] Further, those wherein at least one or two carboxyl groups amongcarboxyl groups of these unsaturated dicarboxylic acids, have become anester, can also be used.

[0062] As a modifying compound which has in the molecule thereof atleast one C—C double bond and a glycidyl group at the same time,allylglycidyl ether, glycidyl acrylate, glycidyl methacrylate, anepoxidized natural oil and fat, etc., are exemplified. Among these,glycidyl acrylate and glycidyl methacrylate are especially preferred.

[0063] As a modifying compound which has in the molecule thereof atleast one C—C double bond and a hydroxyl group at the same time, anunsaturated alcohol having a general formula C_(n)H_(2n-3)OH (n is apositive integer), and an unsaturated alcohol having a general formulaC_(n)H_(2n-5)OH, or C_(n)H_(2n-7)OH (n is a positive integer), etc.,such as allyl alcohol, 4-pentene-1-ol, 1,4-pentadiene-3-ol, etc., areexemplified.

[0064] The above-described modifying compound may be used singly or in acombination.

[0065] An amount of the modifying compound to be added on producing amodified polyphenylene ether is preferably 0.1 to 10 parts by weight,more preferably 0.3 to 5 parts by weight, based on 100 parts by weightof a polyphenylene ether.

[0066] A preferable amount of a radical initiator on producing amodified polyphenylene ether by using the radical initiator ispreferably 0.001 to 1 parts by weight, based on 100 parts by weight of apolyphenylene ether.

[0067] A ratio of the modifying compound added among a modifiedpolyphenylene ether is preferably 0.01 to 5% by weight, more preferably0.1 to 3% by weight.

[0068] In the modified polyphenylene ether, an unreacted modifyingcompound and/or a polymer of the modifying compound may reside. Anamount of the unreacted modifying compound and/or the polymer of themodifying compound which reside in a modified polyphenylene ether ispreferably less than 1% by weight, particularly preferably 0.5% byweight.

[0069] Furthermore, to reduce the amount of the unreacted modifyingcompound and/or the polymer of the modifying compound which reside in amodified polyphenylene ether, on producing the modified polyphenyleneether, if necessary, a compound having an amido bond and/or an aminogroup may be used.

[0070] The compound having an amido bond as herein said, means acompound having a structure of an amido bond {—NH—C(═O)—} in themolecular structure thereof, and a compound having an amino group meansa compound having a structure of {—NH₂} at at least one the terminal endthereof. As a specific example of these compounds, aliphatic amines suchas octyl amine, nonyl amine, tetramethylene diamine, hexamethylenediamine, etc., aromatic amines such as aniline, m-phenylenediamine,p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, etc., aproduct obtainable by reacting the above-described amines with acarboxylic acid or a dicarboxylic acid, etc., lactams such asε-caprolactam, etc., and a polyamide resin, etc., are exemplified, butit is not limited thereto.

[0071] A preferable amount of these compounds having an amido bond or anamino group is 0.001 to 5 parts by weight, preferably 0.01 to 1 parts byweight, more preferably 0.01 to 0.1 parts by weight, based on 100 partsby weight of a polyphenylene ether.

[0072] Moreover, in the present invention, a styrene type thermoplasticresin may be contained in an amount of less than 5 parts by weight basedon 100 parts by weight of the total amount of the polyamide and thepolyphenylene ether.

[0073] The styrene type thermoplastic resin as referred to in thepresent invention, includes a homopolystyrene, a rubber-modifiedpolystyrene (HIPS), a styrene-acrylonitrile copolymer (AS resin), astyrene-rubber-like copolymer-acrylonitrile copolymer (ABS resin).

[0074] When these styrene type thermoplastic resins are formulated in anamount of not less than 5 parts by weight based on 100 parts by weightof the total amount of a polyamide and a polyphenylene ether, electricalconductivity, and a balance of a coefficient of linear expansion and animpact resistance become worsened, and the amount of fines caused bypelletizing, which are generated while processing an extrusion, becomesvery large.

[0075] Further, the additives which are permitted to be added to apolyphenylene ether, may be added in an amount of less than 10 parts byweight based on 100 parts by weight of a polyphenylene ether.

[0076] An impact modifier which can be used in the present invention isa natural or synthetic copolymer material which is an elastomer at aroom temperature (23° C.)

[0077] As a specific example thereof, a natural rubber, a polymer of aconjugated diene compound, a copolymer of an aromatic vinyl compound anda conjugated diene compound, a hydrogenated product of a copolymer of anaromatic vinyl compound and a conjugated diene compound, a polyolefin, apolyester elastomer, a poly-urethane elastomer, a polyamide elastomer,an acrylic ester core-shell copolymer, etc., are mentioned.

[0078] Among these, a copolymer of an aromatic vinyl compound and aconjugated diene compound, a hydrogenated product of a copolymer of anaromatic vinyl compound and a conjugated diene compound, and apolyolefin, are preferred, and a block copolymer of an aromatic vinylcompound and a conjugated diene compound, a hydrogenated product of ablock copolymer of an aromatic vinyl compound and a conjugated dienecompound, and an ethylene-α-olefin copolymer are most preferred.

[0079] The block copolymer of an aromatic vinyl compound and aconjugated diene compound as herein called is a block copolymer composedof a polymer block segment (A) mainly consisting of an aromatic vinylcompound and a polymer block segment (B) mainly consisting of aconjugated diene compound, and the linking structure of each blocks ispreferably at least one selected from the group consisting of an ABtype, an ABA type, and an ABAB type, and more preferably at least oneselected from the group consisting of an ABA type, and an ABAB type.Furthermore, an ABAB type is most preferred since a balance of acoefficient of linear expansion and an impact resistance is excellent.

[0080] The weight ratio of an aromatic vinyl compound and a conjugateddiene compound in the block copolymer is preferably from 10/90 to 90/10,more preferably from 15/85 to 55/45, most preferably from 20/80 to45/55.

[0081] Further, these may be a blend of at least two sorts havingdifferent weight ratios of aromatic vinyl compound to conjugated dienecompound.

[0082] As a specific example of an aromatic vinyl compound, styrene,α-methyl styrene, vinyl toluene, etc., are mentioned, and at least onecompound selected from these is used. Among these, styrene isparticularly preferred.

[0083] As a specific example of a conjugated diene compound, butadiene,isoprene, piperylene, 1,3-pentadiene, etc., are mentioned, and at leastone compound selected from these is used. Among these, butadiene,isoprene, and a combination thereof is preferred.

[0084] When butadiene is employed as a conjugated diene compound in theblock copolymer, concerning a micro-structure of a portion ofpolybutadiene block, a 1,2-vinyl content or the total content of a1,2-vinyl content and a 3,4-vinyl content, is preferably from 5 to 80%,more preferably from 10 to 50%, most preferably from 15 to 40%.

[0085] The hydrogenated product of a block copolymer of an aromaticvinyl compound and a conjugated diene compound means what has beenobtained by conducting a hydrogenation treatment of the above-statedblock copolymer of an aromatic vinyl compound and a conjugated dienecompound and by controlling an aliphatic double bond of a polymer blocksegment mainly consisting of a conjugated diene compound in a range ofover 0 to 100%. A hydrogenated ratio of a hydrogenated product of theblock copolymer is preferably at least 50%, more preferably at least80%, most preferably at least 98%.

[0086] The molecular weight of the block copolymer of an aromatic vinylcompound and a conjugated diene compound, and a hydrogenated productthereof useful in the present invention, is preferably from 10,000 to500,000, most preferably from 40,000 to 250,000, in terms of a numberaverage molecular weight (Mn) as measured at 40° C. with a GPC device[SYSTEM 21] manufactured by Showa Denko Co., using chloroform as asolvent and a polystyrene as a standard thereof.

[0087] Concerning the block copolymer of an aromatic vinyl compound anda conjugated diene compound, at least two sorts thereof having differentlinking styles, having different molecular weights, having differentsorts of an aromatic vinyl compound, having different sorts of aconjugated diene compound, having different 1,2-vinyl contents or1,2-vinyl contents and 3,4-vinyl contents, having different contents ofan aromatic vinyl compound component, or having different hydrogenatedratios, etc., may be used in a mixture.

[0088] An ethylene-α-olefin copolymer which can be used in the presentinvention is a copolymer of ethylene with at least one sort of α-olefinehaving a carbon number of 3 to 20, more preferably a copolymer with atleast one sort of α-olefine having a carbon number of 3 to 16, mostpreferably a copolymer with at least one sort of α-olefine having acarbon number of 3 to 12.

[0089] As an α-olefine copolymerizable with an ethylene unit, propylene,butene-1, pentene-1,4-methylpentene-1, hexene-1, heptene-1, octene-1,nonene-1, decene-1, undecene-1, dodecene-1, tridecene-1, tetradecene-1,pentadecene-1, hexadecene-1, heptadecene-1, octadecene-1, nonadecene-1,or eicosene-1, isobutylene, etc., can be exemplified.

[0090] A preferable content of ethylene in the ethylene-α-olefincopolymer in the present invention is 30 to 95% by weight based on thetotal amount of ethylene-α-olefin copolymer.

[0091] Further, the ethylene-α-olefin copolymer in the present inventionis more preferred to be an ethylene-α-olefin copolymer produced by usinga single site catalyst. The ethylene-α-olefin copolymer produced byusing a single site catalyst, is commercially available, and is alreadyknown. For instance, it is described in JP-B-4-12283, JP-A-60-35006,JP-A-60-35007, JP-A-60-35008, JP-A-5-155930, JP-A-3-163088, and U.S.Pat. No. 5,272,236.

[0092] The single site catalyst is a metallocene catalyst containing 1to 3 molecules of cyclopentadienyl or a substituted cyclopentadienyl ora catalyst geometrically controlled of which a property of an activepoint is uniform.

[0093] A polymerization method of the ethylene-α-olefin copolymer in thepresent invention can be conducted by a gas phase method or a solutionmethod as shown in the above-described publications. A preferablepolymerization method is a solution method.

[0094] The molecular weight of the ethylene-α-olefin copolymer in thepresent invention, is preferably not lower than 10,000, more preferablyfrom 10,000 to 100,000, most preferably from 20,000 to 60,000, in termsof a number average molecular weight (Mn) as measured at 140° C. with adevice: 150c-GPC manufactured by WATERS Co., using1,2,4-trichlorobenzene as a solvent and a polystyrene as a standardthereof.

[0095] The molecular weight distribution (weight average molecularweight/number average molecular weight: Mw/Mn) of the ethylene-α-olefincopolymer in the present invention, as measured by the above stated GPC,is preferably not higher than 3, and is more preferably from 1.8 to 2.7.

[0096] An impact modifier which can be used in the present invention,may be a wholly or a partly modified impact modifier.

[0097] The modified impact modifier referred to herein means an impactmodifier which has been modified with at least one sort of a modifyingcompound which has in the molecular structure thereof at least one C—Cdouble bond or triple bond, and has at least one of a carboxyl acidgroup, an acid anhydride group, an amino group, a hydroxyl group, or aglycidyl group.

[0098] As a method for producing the modified impact modifier,

[0099] (1) a method for reacting it with the modifying compound bymelting and kneading in the presence or absence of a radical initiator,and in the range of temperature of not lower than a softeningtemperature of the impact modifier and not higher than 250° C.,

[0100] (2) a method for reacting in a solution an impact modifier withthe modifying compound in a presence or absence of a radical initiator,at a temperature of not higher than the softening temperature of theimpact modifier,

[0101] (3) a method for reacting an impact modifier with the modifyingcompound in a presence or absence of a radical initiator, at atemperature of not higher than the softening temperature of the impactmodifier, and without melting the impact modifier and the modifyingcompound, etc., are exemplified.

[0102] Any of these methods may be usable, but the method of (1) ispreferable, and further in the method of (1), conducted in the presenceof a radical initiator, is most preferable.

[0103] The at least one sort of a modifying compound which has, in themolecular structure thereof, at least one C—C double bond or triplebond, and has at least one of a carboxyl acid group, an acid anhydridegroup, an amino group, a hydroxyl group, or a glycidyl group, as hereinso called, means the same as the modifying compound mentioned concerningthe modified polyphenylene ether.

[0104] Further, as the impact modifier of the present invention, whathas preliminarily been mixed with an oil having a paraffin as a maincomponent thereof, may be used. By preliminarily mixing with an oilhaving a paraffin as a main component thereof, a balance of acoefficient of linear expansion and an impact resistance, can further bevery usefully improved.

[0105] The preferable amount of oil is not more than 70 parts by weight,based on 100 parts by weight of the impact modifier. When more than 70parts by weight is present, the handling property thereof is inferior.

[0106] The oil having a paraffin as a main component thereof, referredto herein, means a mixture of a hydrocarbon type compound comprised ofthree combined components of a compound containing an aromatic ring, acompound containing a naphthenic ring, and a paraffin type compound, andhaving a weight average molecular weight of a range of 500 to 10000,which has a content of the paraffin type compound of not lower than 50%by weight.

[0107] More preferably, it is comprised of 50 to 90% by weight of aparaffin type compound, 10 to 40% by weight of a compound containing anaphthenic ring, and not more than 5% by weight of a compound containingan aromatic ring.

[0108] The oil having a paraffin as a main component thereof iscommercially available, such as for example, PW 380, manufactured byIdemitsu Kosan Co., Ltd., is mentioned.

[0109] Non-limiting examples of a method of mixing the above-describedoil with an aromatic impact modifier include: a method wherein apredetermined amount of a paraffin type oil is added to the impactmodifier having a shape of pellet or powder to become uniform, and isleft to stand; and a method wherein a predetermined amount of a paraffintype oil is added on the way of an extruder, and is melted and kneaded.

[0110] A carbon type filler for an electrically conductive use, whichcan be used in the present invention, is a carbon type filler which isused for the purpose to provide a non-electrically conductive materialwith an electrically conductive property, whose shape may be, that of aparticle, a flake, or a fiber.

[0111] As an example thereof, a carbon black, a nanotube carbon, acarbon fiber, and graphite, for an electrically conductive use can beused, and among these, a carbon black for an electrically conductive useis most suitable.

[0112] A carbon black for an electrically conductive use, which can beused in the present invention, is a carbon black having an amount ofabsorbing dibutyl phthalate (DBP) of not less than 250 ml/100 g,preferably having an amount of absorbing dibutyl phthalate (DBP) of notless than 300 ml/100 g, more preferably having an amount of absorbingdibutyl phthalate (DBP) of not less than 350 ml/100 g. The amount ofabsorbed DBP as stated herein, means a value as measured by the methodas determined by ASTM D 2414.

[0113] Further, as a carbon black for an electrically conductive use,according to the present invention, a carbon black having a BET surfacearea of not smaller than 200 m²/g, is preferred, and that having a BETsurface area of not smaller than 400 m²/g is more preferred.

[0114] As a carbon black for an electrically conductive use which iscommercially available, a Ketjen black EC-600JD [an amount of absorbingDBP=495 ml/100 g, and a BET surface area=1270 m²/g] and a Ketjen blackEC [an amount of absorbing DBP=360 ml/100 g, and a BET surface area=800m²/g] manufactured by Ketjen Black International Co., are exemplified.

[0115] A carbon black for an electrically conductive use of the presentinvention, does not include a carbon black for a general coloring use.The carbon black for a coloring use is that having the above statedamount of absurbed DBP of less than 250 ml/100 g, and a BET surface areaof less than 200 m²/g.

[0116] In the present invention, when a carbon black for coloring use isemployed instead of a carbon black for an electrically conductive use,which is made to reside in a phase of a polyphenylene ether, electricalconductivity, and the balance of coefficient of linear expansion andimpact resistance all become worse. Furthermore, the amount of finescaused by pelletizing, which are generated while processing anextrusion, increases.

[0117] A nanotube carbon which can be used in the present inventionmeans a hollow carbon type fiber having a diameter not larger than 1 μm,which also includes that having a shape of a coil wherein a spiral has apitch of not greater than 1 μm.

[0118] A carbon fiber which can be used in the present inventionincludes all fibers which are obtained by calcinating and carbonizing inan inert atmosphere at a temperature of 1000° C. to 3500° C. a fiberwherein a polyacrylonitrile (PAN), a pitch, etc. were used as a rawmaterial. A preferable diameter of the fiber is 3 to 30 μm, 5 to 20 μmis more preferred.

[0119] A graphite which can be used in the present invention includesnot only what is obtained by heating anthracite, or pitch, etc. at ahigh temperature in an arc furnace, but also a graphite which isnaturally produced. Graphite particles preferably have an averagediameter of 0.1 to 50 μm, more preferably 1 to 30 μm.

[0120] These carbon type fillers for an electrically conductive use, maysurely be improved with respect to their adhesion property with a resinor with respect to their handling property by using various known kindsof coupling agents and/or sizing agents.

[0121] In the present invention, an amount of the carbon type filler foran electrically conductive use, is preferred to be in the range of 0.5to 50 parts by weight based on 100 parts by weight of a mixture mainlycomposed of 40 to 90 parts by weight of a polyamide, 5 to 50 parts byweight of a polyphenylene ether, and 5 to 30 parts by weight of animpact modifier.

[0122] In the present invention, a metallic salt as represented by thefollowing formula, may be used.

M^(y+) _(n)X^(z−) _(n·y/z)

[0123] wherein M^(y+) represents at least one metallic ion selected fromthe group consisting of copper, nickel, tin, cerium and an alkalinemetal, and X^(z−) represents a negatively charged ion of a halide ionsuch as Cl, Br, F, I, etc., or a carboxylate ion, such as a stearate, anacetate, etc., n is an integer of 1 to 6, y is an integer indicatingelectric charge of a positive ion of M, and z is an integer indicatingelectric charge of a negative ion of X.

[0124] By formulating the above-described metallic salt to thecomposition of the present invention, an adhesion property with a coatafter coating can be made to be strong.

[0125] Preferable as M^(y+) in the formula are copper and/or an alkalinemetal ion, and an alkaline metal ion is most preferable. Most preferableas X^(z−) is a halogen ion, especially an iodine ion and/or a bromineion are preferable. An iodine ion is most preferable.

[0126] As a specific example of the metallic salt which can be used inthe present invention, copper iodide, copper chloride, copper acetate,potassium iodide, cerium stearate, etc. are mentioned. Among these,copper iodide, potassium iodide, copper bromide, potassium bromide, andsodium iodide, are more preferable. Potassium iodide and sodium iodide,are most preferable. They may be used in combination.

[0127] A formulated amount of the metallic salt, is preferably an amountof less than 2 parts by weight based on 100 parts by weight of the totalamount of a polyamide, a polyphenylene ether, an impact modifier, and acarbon type filler for an electrically conductive use, preferably of0.001 to 1 parts by weight, more preferably of 0.001 to 0.5 parts byweight.

[0128] As a method of adding this metallic salt, (1) a method of addinga metallic salt on a polymerization of a polyamide to be used, (2) amethod of adding in a form of a master batch wherein a metallic salt hasbeen preliminarily mixed with the whole or a part of a polyamide(preliminarily formulated with a polyamide in a high concentration), (3)a method of directly adding a metallic salt when a composition isproduced, etc., are exemplified. Any of the methods may be usable, butthe methods of (1) or (2) is preferable. A combination of these methodsalso is surely possible.

[0129] Further, in the present invention, a compatibilizer may be usedwhen the composition is produced.

[0130] A main purpose of using the compatibilizer is to improve aphysical property of a polyamide-polyphenylene ether mixture. Thecompatibilizer which can be used in the present invention means amultifunctional compound which interacts with a polyphenylene ether, apolyamide, or both of them. The interaction may be chemical (forexample, grafting), or physical (for example, a change of a surfaceproperty of a dispersion phase). In any case the resultantpolyamide-polyphenylene ether mixture exhibits an improvedcompatibility.

[0131] Examples of various kinds of a compatibilizer which can be usedwhen the present invention is conducted, as is explained below include:a liquid diene polymer, a polymer containing a functional group, anepoxy compound, a polyolefin oxide wax, quinones, an organosilanecompound, and a multifunctional compound.

[0132] Examples of a liquid diene polymer which can be suitably used inthe present invention include: a homopolymer of a conjugated diene, anda copolymer of a conjugated diene with at least one monomer selectedfrom the group consisting of another conjugated diene, a vinyl monomer(for example, styrene and α-methylstyrene), an olefin (for example,ethylene, propylene, butene-1, isobutylene, hexene-1, octene-1, anddodecene-1), and a mixture of these. The number average molecular weightthereof is from 150 to 10,000, preferably from 150 to 5,000. Thesehomopolymers and copolymers can be produced, for instance, by themethods as described in U.S. Pat. Nos. 4,054,612, 3,876,721, and3,428,699. Among these polymers, particularly a polybutadiene, apolyisoprene, a poly(1,3-pentadiene), a poly(butadiene-isoprene), apoly(styrene-butadiene), a polychloroprene, apoly(butadiene-α-methylstyrene), a poly(butadiene-styrene-isoprene), apoly(butylene-butadiene), etc., are exemplified.

[0133] As a polymer containing a functional group, which can be suitablyused in the present invention, a copolymer of an aromatic vinyl compoundwith a vinyl compound containing at least one sort of a functional groupwhich has in the molecular structure thereof at least one C—C doublebond or triple bond, and at least one of a carboxylic acid group, anacid anhydride group, an amino group, a hydroxyl group, or a glycidylgroup, is exemplified. The vinyl compound containing at least one sortof a functional group which has in the molecular structure thereof atleast one C—C double bond or triple bond, and at least one of acarboxylic acid group, an acid anhydride group, an amino group, ahydroxyl group, or a glycidyl group, is the same as the one which can beused as a modifying compound of a polyphenylene ether, and at least oneselected from these can be used. Among these, maleic anhydride, glycidylacrylate and glycidyl methacrylate are preferred. As an example of anaromatic vinyl compound, styrene, α-methylstyrene, vinyltoluene, etc.,are exemplified, and at least one selected from these can be used. Amongthem, styrene is particularly preferred. Among these polymers containinga functional group, a styrene-maleic anhydride copolymer is mostpreferred.

[0134] As an epoxy compound, which can be suitably used in the presentinvention, (1) an epoxy resin which can be prepared by condensing apolyhydric phenol (for example, bisphenol A, tetrabromobisphenol A,resorcinol, and hydroquinone) and epichlorohydrine, (2) an epoxy resinwhich can be prepared by condensing a polyhydric alcohol (for example,ethylene glycol, propylene glycol, butylene glycol, a polyethyleneglycol, a polypropylene glycol, pentaerythritol, and trimethylolethane,etc.) and epichlorohydrine, (3) a glycidyl etherified product ofmonohydric alcohols and monohydric phenols, for example, phenyl glycidylether, butylglycidyl ether, and cresylglycidyl ether, (4) a glycidylderivative of an amino compound, for example, a glycidyl derivative ofaniline, and (5) an epoxidized product of a higher olefin orcycloalkene, or a natural unsaturated oil (for example, a soy bean) andan epoxidized product of the liquid diene polymer, are exemplified.

[0135] A polyolefin oxide wax, which is suitably used in the presentinvention, is known, and an explanation thereof and a producing methodthereof are described in U.S. Pat. Nos. 3,822,227, and 3,756,999, andGerman Patent Publication Examined No. 3047915, and No. 2201862.Generally, they are produced by an oxidation, or an oxidation insuspension of a polyolefin.

[0136] A characteristic feature of a quinone compound, which is suitablyused in the present invention, is as follows. That is, it has at leastone 6 membered carbon ring in the molecule of an unsubstitutedderivative, has at least two carbonyl groups in the ring structure (bothof them may be in the same ring, and may be in a different ring, when ithas at least two rings, provided that they occupy the positioncorresponding to a 1,2-position or a 1,4-position in a quinone having asingle ring), and has at least two C—C double bond in the ring structure(this C—C double bond and a C—O double bond in carbonyl reside in thering structure, and the C—C double bond and a C—O double bond incarbonyl are conjugated each other). When at least two rings reside inan unsubstituted quinone, these rings may be condensed non-condensed orboth. Each other of non-condensed ring may be linked by the C—C doublebond directly, or a hydrocarbon group having conjugated unsaturated bondsuch as ═C—C═.

[0137] Further, a substituted quinone is also included in the presentinvention. When the substitution is desired, the degree of substitutionmay be from 1 to the maximum number of a hydrogen atom which can besubstituted. As an example of a various kinds of a substituted groupswhich can reside in a structure of a non-substituted quinone, a halogensuch as chlorine, bromine, fluorine, etc., a hydrocarbon group such as abranched or non-branched, or a saturated or unsaturated alkyl group, anaryl group, an alkyl aryl group, a cycloalkyl group, a halogenatedderivative thereof, and a similar hydrocarbon group thereto having ahetero atom such as particularly oxygen, sulfur, or phosphorus (thesegroups link to a quinone ring via the hetero atom, such as by an oxygenbond), are exemplified.

[0138] Examples of various kinds of quinones include: 1,2-benzoquinone,1,4-benzoquinone, 2,6-diphenylquinone, tetramethyldiquinone,2,2′-diphenoquinone, 4,4′-diphenoquinone, 1,2-naphtoquinone,1,4-naphtoquinone, 2,6-naphtoquinone, chloranils,2-chloro-1,4-benzoquinone, and 2,6-dimethylbenzoquinone, etc.

[0139] A characteristic feature of an organosilane compound, which issuitably used as a compatibilizer of the present invention, is that ithas in the molecule thereof (a) at least one silicon atom linked withcarbon via an oxygen bond, and (b) at least one of a C—C double bond, aC—C triple bond or a functional group selected from the group consistingof an amine group and a mercapto group (provided that these functionalgroups do not directly link to a silicon atom).

[0140] In these compounds, the moiety, C—O—Si, usually resides as analkoxyl group or an acetoxyl group which is directly linked with asilicon atom, and the alkoxyl group and the acetoxyl group generallyhave a number of carbon atoms of less than 15, and may contain a heteroatom (for example, oxygen). Moreover, in these compounds, at least twosilicon atoms may reside, and when so many of silicon atoms reside, theylink via an oxygen bond (for example, a siloxane), a silicon bond, or abifunctional organic group (for example, a methylene group and aphenylene group).

[0141] Examples of suitable organosilane compounds include,γ-aminopropyltriethoxysilane, 2-(3-cyclohexanyl)ethyltrimethoxysilane,1,3-divinyl tetraethoxysilane, vinyl tris-(2-methoxyethoxy)silane,5-bicycloheptenyl triethoxysilane, and γ-mercaptopropyltrimethoxysilane.

[0142] Multifunctional compounds, which are suitable as a compatibilizerof the present invention, are of three types. The first type of amultifunctional compound has in the molecule thereof, both (a) a C—Cdouble bond or a C—C triple bond, and (b) at least one of a carboxylicacid group, an acid anhydride group, an acid halide group, an anhydridegroup, an acid halide anhydride group, an acid amide group, an acidester group, an imido group, an amino group, or a hydroxyl group.Examples of a multifunctional compound include amongst others: a maleicacid, a maleic anhydride, a fumaric acid, a citraconic acid, an itaconicacid, a maleimide, a maleic hydrazide, a reaction product of diamine andcarboxylic acids selected from a maleic anhydride, a maleic acid, afumaric, acid, etc., a dichloromaleic anhydride, a maleic amide, anunsaturated dicarboxylic acid (for example, an acrylic acid, a butenicacid, a methacrylic acid, a t-ethylacrylic acid, a pentenic acid, adecenic acid, an undecenic acid, a dodecenic acid, a linolic acid,etc.), an ester, an acid amide or anhydride of the above-describeddicarboxylic acids, an unsaturated alcohol (for example, an alkylalcohol, a crotyl alcohol, a methyl vinyl calbinol, 4-pentene-1-ol,1,4-hexadiene-3-ol, 3-butene-1,4-diol, 2,5-dimethyl-3-hexene-2,5-diol,and alcohols having the formulae of C_(n)H_(2n-5)OH, C_(n)H_(2n-7)OH,and C_(n)H_(2n-9)OH, (provided that n is a positive integer to 30), anunsaturated amine obtainable by replacing a —OH group (one or plural) ofthe above-described unsaturated alcohol with an NH₂ group, and a dienepolymer and a diene copolymer which are provided with a functionalgroup. Among these, a compatibilizer, which is preferred for thecomposition of the present invention, is a maleic anhydride, and afumaric acid. This type of a compatibilizer can be preliminarily mixedwith a polyphenylene ether in the composition of the present invention.

[0143] A compound of a multifunctional compatibilizer of the secondgroup, which is suitably used in the present invention, is characterizedby possessing both (a) a group represented by the formula (OR) (in theformula, R is a hydrogen, an alkyl group, an aryl group, an acyl group,or a carbonyldioxyl group.), and (b) at least two groups selected fromthe group consisting of a carboxylic acid, an acid halide, an acidanhydride, an anhydride, an acid halide anhydride, an acid ester, anacid amide, an imido, an amino, and a salt thereof, which may be thesame or different. A typical example of a compatibilizer of this groupis an aliphatic polycarboxylic acid, an ester thereof, and an acid amidethereof, represented by the following formula.

(R^(I)O)_(m)R(COOR^(II))_(n)(CONR^(III)R^(IV))_(s)

[0144] wherein R is a linear or a branched saturated aliphatichydrocarbon having carbon atoms of 2 to 20, preferably of 2 to 10, R^(I)is hydrogen, or is selected from the group consisting of an alkyl group,an aryl group, an acyl group and a carbonyldioxy group, having 1 to 10carbon atoms, preferably 1 to 6, most preferably 1 to 4, R^(II) is eachindependently hydrogen, or is selected from the group consisting of analkyl group and an aryl group, having 1 to 20 carbon atoms, preferably 1to 10, R^(III) and R^(IV) is each independently hydrogen, or is selectedfrom the group consisting essentially of an alkyl group and an arylgroup, having 1 to 10 carbon atoms, preferably 1 to 6, most preferably 1to 4, m equals to 1, (n+s) is at least 2, preferably equals to 2 or 3,and each of n and s is at least 0. Further, (OR^(I)) locates at theposition of α or β to a carbonyl group, and at least two carbonyl groupsare separated by 2 to 6 carbon atoms. Apparently, R^(I), R^(II), R^(III)and R^(IV) cannot be an aryl when a substituent of these has less than 6carbon atoms.

[0145] Polycarboxylic acid useful in the present invention areexemplified, and can be used in the form of commercial products such asan anhydride, a hydrated acid, etc. suitable polycarboxylic acids are:citric acid, a malic acid, and an agaric acid, are exemplified. Amongthese, citric acid and malic acid are the preferred compatibilizers.

[0146] Examples of acid esters, useful in the present invention,include: acetyl citrate, and monostearyl citrate and/or distearylcitrate.

[0147] Examples of acid amides, useful and suitable in the presentinvention include: N,N′-diethyl citric amide, N-phenyl citric amide,N-dodecyl citric amide, N,N′-didodecyl citric amide, and N-dodecyl malicamide.

[0148] The characteristic feature of a compound of a multifunctionalcompatibilizer of the third group, which is suitably used in the presentinvention, is that it possesses, in the molecule thereof, both of (a) anacid halide group, most preferably, an acid chloride group, and (b) atleast one group consisting of a carboxylic acid group, a carboxylic acidanhydride group, and an acid ester group, or an acid amide group,preferably, of a carboxylic acid group, and a carboxylic acid anhydridegroup.

[0149] Examples of a compatibilizer which fall in this group include: atrimellitic acid anhydride halide, a chloroformylsuccinic acidanhydride, a chloroformylsuccinic acid, a chloroformylglutaric acidanhydride, a chloroformylglutaric acid, a chloroacetylsuccinic acidanhydride, a chloroacetylsuccinic acid, a trimellitic acid halide, and achloroacetylglutaric acid.

[0150] Furthermore, the above compatibilizer can be prereacted with atleast one portion of the polyphenylene ether to use the compatibilizeras a PPE-functionalized compound.

[0151] The above-described compatibilizers are respectively described inU.S. Pat. Nos. 4,315,086, and 4,642,358. The above-describedcompatibilizers may be used alone, or may optionally be used incombination. Further, they may be directly added on melting andkneading, or they may be made to preliminarily react with either one orboth of a polyphenylene ether and a polyamide, or with another resinousmaterial which is used on production of the composition of the presentinvention.

[0152] A preferable amount of the compatibilizer is 0.01 to 20 parts byweight based on 100 parts by weight of the amount of a mixture of apolyamide and a polyphenylene ether, and a more preferable one is 0.1 to10 parts by weight.

[0153] In the present invention, besides the above-described components,if necessary, an additive component may be added, so long as it does notharm the effect of the present invention.

[0154] Examples of the additive component are enumerated as follows.

[0155] That is, another thermoplastic resin such as a polyester, apolyolefin, etc., an inorganic filler (talc, kaolin, xonotlite,wollastonite, titanium oxide, potassium titanate, a carbon fiber, aglass fiber, etc.), known silane coupling agents to enhance affinitybetween an inorganic filler and a resin, a flame retardant (ahalogenated resin, a silicone type flame retardant, magnesium hydroxide,aluminium hydroxide, an organic phosphoric ester compound, ammoniumpolyphosphate, red phosphorus, etc.), a fluorine type polymer showing apreventing effect of dropping, a plasticizer (an oil, a low molecularweight polyolefin, a polyethylene glycol, a fatty ester, etc.), anassistant to a flame retardant such as antimony trioxide, etc., variouskinds of a peroxide, zinc oxide, zinc sulfide, an antioxidant, anultraviolet absorber, a light stabilizer, etc., are exemplified.

[0156] The additive component may be added in a range of not exceedingin total 50 parts by weight based on 100 parts by weight of the totalamount of (A) to (C) components.

[0157] Further, a component which is recommended to reside in a phase ofa polyamide (an additive such as a nuclear agent for polyamide, a slipagent, various kinds of dyes, titanium oxide, a pigment such as carbonblack for coloring, a mold releasing agent, etc.) may be addedrespectively in a range not exceeding 10 parts by weight based on 100parts by weight of the total amount of (A) to (C) components. Theadditive component of these can surely be used in a combination of atleast two kinds thereof.

[0158] The most important matter in the present invention is that thecarbon type filler for an electrically conductive use resides in a phaseof a polyphenylene ether.

[0159] Further, in a case where the composition of the present inventionforms a morphology of dispersion so that the impact modifier is includedin a phase of the polyphenylene ether, it is preferable that among allof fillers for an electrically conductive use, most thereof resideoutside of the impact modifier, but not more than the largest half ofall of the carbon type fillers for an electrically conductive use whichreside in the phase of the polyphenylene ether, may be contained in theimpact modifier.

[0160] When the carbon type fillers for an electrically conductive usedo not reside in a phase of a polyphenylene ether, and, for instance,most thereof reside in a phase of a polyamide, and/or an impactmodifier, a balance of a coefficient of linear expansion and an impactresistance, and fluidity are caused to deteriorate, and an amount offines caused by pelletizing, which are generated when processing ofextrusion is conducted, becomes very large.

[0161] Confirmation that the carbon type filler for an electricallyconductive use resides in a phase of a polyphenylene ether, can bedetermined by the methods as follows.

[0162] (1) A central part of a sample of pellet is cut into anultra-thin slice with an ultra-microtome so as to observe a flowingdirection. Conditions of cutting include: a temperature not higher than0° C., preferably not higher than −30° C., a thickness of the slice: 60to 80 nm)

[0163] (2) The ultra-thin slice prepared is left to stand for 5 to 60min. in an atmosphere of a vapor of ruthenium tetroxide, and is dyed.

[0164] (3) The dyed ultra-thin slice is observed at a magnification ofabout 20,000 with a transmission electron microscope.

[0165] In this condition, a phase showing a grey color is a phase of apolyphenylene ether, and a phase of an impact modifier shows non-dyedcolor (white) or black depending upon the kinds thereof.

[0166] Presence of a carbon type filler for an electrically conductiveuse, for instance, when the carbon type filler for an electricallyconductive use is a carbon black for an electrically conductive use, isobserved by an appearance of particles interspersed. The appearances aredifferent depending upon the kinds of a carbon type filler for anelectrically conductive use, but discrimination thereof can be easilydetermined from difference of a morphology of a dispersion by a personskilled in the art.

[0167] In the present invention, a preferable ratio of particles of apolyphenylene ether, wherein a carbon type filler for an electricallyconductive use resides, based on all particles of a polyphenylene ether,is preferred to satisfy the following equation.

R≧(t/r)

[0168] wherein R represents the ratio of an amount of particles of apolyphenylene ether, wherein a carbon type filler for an electricallyconductive use resides, based on an amount of all particles of apolyphenylene ether, as shown in an electron microscope photograph whichwas taken at a magnification of 20,000 in a range of 50 μm² or broader,r represents an average diameter(nm) of a dispersion of a polyphenyleneether in a direction of a minor axis, and t represents a thickness ofthe ultra-thin slice,

[0169] When the morphology is such that an impact modifier is includedin a phase of a polyphenylene ether, presence of a carbon type filler,for an electrically conductive use, in the impact modifier can berecognized by observing a non-dyed ultra-thin slice with a transmissionelectron microscope.

[0170] A preferable method for causing the carbon type filler for anelectrically conductive use to reside in a phase of a polyphenyleneether, which is a characteristic feature of the present invention, is topreliminarily mix and knead the carbon type filler for an electricallyconductive use with the impact modifier.

[0171] Particularly, it is more effective to add the carbon type fillerfor an electrically conductive use in a form of a master batch whereinit has been preliminarily mixed and kneaded with the impact modifier.

[0172] A suitable amount of the carbon type filler for an electricallyconductive use which is preliminarily mixed and kneaded with the impactmodifier, is at least 10% by weight, preferably at least 30% by weight,more preferably at least 50% by weight, based on all of the carbon typefiller used for an electrically conductive use.

[0173] Further, the ratio of the carbon type filler for an electricallyconductive use and the impact modifier, is preferably 3 to 50 parts byweight, more preferably 5 to 30 parts by weight, of the carbon typefiller for an electrically conductive use, based on 100 parts by weightof the impact modifier.

[0174] When the carbon type filler for an electrically conductive use ispreliminarily mixed and kneaded with the impact modifier, apolyphenylene ether may be made to reside therein. When thepolyphenylene ether is made to reside therein, the suitable amount of apolyphenylene ether in a mixture of an impact modifier and apolyphenylene ether is preferably not more than 90% by weight, morepreferably not more than 70% by weight, most preferably not more than50% by weight.

[0175] To cause a carbon type filler for an electrically conductive useto reside in a phase of a polyphenylene ether, when the amount of thepolyphenylene ether in a mixture of the impact modifier and thepolyphenylene ether is made to be not less than 90% by weight, anincrease of a melting viscosity is incurred, and a processing propertybecomes inferior.

[0176] The reason why a carbon type filler for an electricallyconductive use resides in a phase of a polyphenylene ether, although thecarbon type filler for an electrically conductive use is added in a formof a master batch wherein the filler has been preliminarily mixed andkneaded with an impact modifier, is thought to be as follows, though itis only a presumption.

[0177] Generally, secondary amines are provided at the terminal ends ofa polyphenylene ether, and the secondary amines raises an interactionwith a carboxylic acid group, etc. residing on a surface, for instance,of a carbon black for an electrically conductive use. It is presumedthat due to the interaction, the carbon type filler for an electricallyconductive use becomes easy to stably reside in a polyphenylene ether.

[0178] As a specific processing machine to obtain the composition of thepresent invention, for instance, a monoaxial extruder, a biaxialextruder, a roll, a kneader, a Brabender Plastograph, a Bambury mixer,etc., are mentioned. Among them, a biaxial extruder is preferable, andparticularly a biaxial extruder, which is provided with a feed openingat an upstream side and at least one feed opening at a downstream side,is most preferable.

[0179] A temperature of mixing and kneading thereon is not especiallylimited, but, a condition so that a suitable composition can be obtainedmay be optionally selected from the range of 240 to 360° C.

[0180] Specific methods of the present invention include: (1) a methodwherein an impact modifier, a carbon type filler for an electricallyconductive use, and a polyphenylene ether are supplied from a feedopening at an upstream side, and are mixed and kneaded, and then apolyamide is supplied from a feed opening at a downstream side, and aremixed and kneaded, (2) a method wherein an impact modifier, a part of acarbon type filler for an electrically conductive use, and apolyphenylene ether are supplied from a feed opening at an upstreamside, and are mixed and kneaded, and then a polyamide and the rest of acarbon type filler for an electrically conductive use are supplied froma feed opening at a downstream side, and are mixed and kneaded, (3) amethod wherein a part of an impact modifier, a carbon type filler for anelectrically conductive use, and a polyphenylene ether are supplied froma feed opening at an upstream side, and are mixed and kneaded, and thena polyamide and the rest of an impact modifier are supplied from a feedopening at a downstream side, and are mixed and kneaded, (4) a methodwherein a part of an impact modifier, a part of a carbon type filler foran electrically conductive use, and a polyphenylene ether are suppliedfrom a feed opening at an upstream side, and are mixed and kneaded, andthen a polyamide, the rest of an impact modifier, and the rest of acarbon type filler for an electrically conductive use, are supplied froma feed opening at a downstream side, and are mixed and kneaded, (5) amethod wherein a master batch having been obtained by preliminarilymixing and kneading an impact modifier and a carbon type filler for anelectrically conductive use, and a polyphenylene ether are supplied froma feed opening at an upstream side, and are mixed and kneaded, and thena polyamide is supplied from a feed opening at a downstream side, andare mixed and kneaded, (6) a method wherein a master batch having beenobtained by preliminarily mixing and kneading an impact modifier and apart of a carbon type filler for an electrically conductive use, and apolyphenylene ether are supplied from a feed opening at an upstreamside, and are mixed and kneaded, and then a polyamide and the rest of acarbon type filler for an electrically conductive use are supplied froma feed opening at a downstream side, and are mixed and kneaded, (7) amethod wherein a master batch having been obtained by preliminarilymixing and kneading three kinds of an impact modifier, a part of apolyphenylene ether and a part of a carbon type filler for anelectrically conductive use, and the rest of a polyphenylene ether aresupplied from a feed opening at an upstream side, and are mixed andkneaded, and then a polyamide and the rest of a carbon type filler foran electrically conductive use are supplied from a feed opening at adownstream side, and are mixed and kneaded, (8) a method wherein amaster batch having been obtained by preliminarily mixing and kneadingan impact modifier and a part of a carbon type filler for anelectrically conductive use, and a polyphenylene ether are supplied froma feed opening at an upstream side, and are mixed and kneaded, and thena part of a polyamide, and a master batch having been obtained bypreliminarily mixing and kneading the rest of a polyamide and the restof a carbon type filler for an electrically conductive use, are suppliedfrom a feed opening at a downstream side, and are mixed and kneaded. Amethod of using a master batch as in (5) to (8) is preferred, but anymethod may be used so long as a carbon type filler for an electricallyconductive use, resides in the polyphenylene ether phase.

[0181] A temperature of mixing and kneading on producing a master batchis not especially limited, but, a condition so that a suitablecomposition can be obtained may be optionally selected from the range of150 to 300° C.

[0182] The composition of the present invention thus obtainable can bemolded to produce molded articles of various kinds, by variousconventionally known methods, for instance, such as injection molding,extrusion molding, and blow molding.

[0183] The composition of the present invention can be used to producearticles such as a exterior parts of a motorbike, such as a cowl, etc.;for interior parts of an automobile, for exterior panels or exteriorparts of an automobile, such as a fender, a door panel, a front panel, arear panel, a locker panel, a rear bumper panel, a back door garnish, anemblem garnish, a panel for a feeding port of a fuel, an over fender, anouter door handle, a door mirror housing, a bonnet air intake, a bumper,a bumper guard, a roof rail, a roof rail leg, a pillar cover, a wheelcover; for various kinds of air parts, etc., and in parts of an IC tray,etc.; in the electrical or electronic fields. Among them, thecomposition is particularly suitably for exterior automobile parts whichare to be subjected to electrostatic coating.

EXAMPLES

[0184] Hereinafter, the present invention is explained in detail byreferring to examples and comparative examples.

[0185] A Raw Material Used:

[0186] (1) A polyphenylene ether

[0187] Poly(2,6-dimethyl-1,4-phenylene ether)

[0188] (1-1) A reduced viscosity (measured as a 0.5 g/dl of chloroformsolution, at 30° C.)=0.52 dl/g (hereinafter abbreviated as “PPE-H”)

[0189] (1-2) A reduced viscosity=0.42 dl/g (hereinafter abbreviated as“PPE-L”)

[0190] (2) A polyamide

[0191] (2-1) A polyamide 6,6 resin (hereinafter abbreviated as “PA-66”)

[0192] A number average molecular weight=16,000

[0193] A concentration of a terminal amino group=50 m equivalent/kg

[0194] A concentration of a terminal carboxyl group=80 m equivalent/kg

[0195] This contains as a minute amount of component, 100 ppm of acopper type thermal stabilizer and 800 ppm of a slip agent (a salt of ametallic stearate).

[0196] (2-2) A polyamide 6 resin (hereinafter abbreviated as “PA-6”)

[0197] A relative viscosity in a sulfuric acid (1 g of a polymer/100 mlof a 98% of sulfuric acid, measured at 25° C.)=2.6

[0198] A concentration of a terminal amino group=45 m equivalent/kg

[0199] A concentration of a terminal carboxyl group=65 m equivalent/kg

[0200] (2-3) A polyamide 6,6 resin (hereinafter abbreviated as “PA-66L”)

[0201] A number average molecular weight=9,100

[0202] A concentration of a terminal amino group=55 m equivalent/kg

[0203] A concentration of a terminal carboxyl group=65 m equivalent/kg

[0204] This contains as a minute amount of component, 100 ppm of acopper type thermal stabilizer and 800 ppm of a slip agent (a salt of ametallic stearate).

[0205] (3) An impact modifier

[0206] (3-1) An ethylene-octene copolymer (hereinafter abbreviated as“EOR”)

[0207] A content of octene=24% by weight

[0208] MFR=30 g/10 min. (measured at 190° C., and 2.16 kg of a load)

[0209] mp=60° C. (a DSC method, a speed of raising temperature 10°C./min.)

[0210] (3-2) A modified product of an ethylene-octene copolymer with amaleic anhydride (hereinafter abbreviated as “MEOR”)

[0211] A content of octene=28 wt %

[0212] MFR=0.8 g/10 min. (measured at 190° C., and 2.16 kg of a load)

[0213] mp=55° C. (a DSC method, a speed of raising temperature 10°C./min.)

[0214] A ratio of a maleic anhydride added=1.0 wt %

[0215] (3-3) A 3 type hydrogenated styrene-butadiene copolymer having ahigh molecular weight (hereinafter abbreviated as “HTR1”)

[0216] A linking style=3 type (ABA type) block

[0217] [component A is a styrene block, and component B is a butadieneblock.]

[0218] A styrene content=33 wt %

[0219] A total amount of a vinyl content=33 wt %

[0220] A number average molecular weight=150,000

[0221] (3-4) A 3 type hydrogenated styrene-butadiene copolymer having alow molecular weight (hereinafter abbreviated as “HTR2”)

[0222] A linking style=3 type (ABA type) block

[0223] [component A is a styrene block, and component B is a butadieneblock.]

[0224] A styrene content=29 wt %

[0225] A total amount of a vinyl content=32 wt %

[0226] A number average molecular weight=51,000

[0227] (3-5) A 4 type hydrogenated styrene-butadiene copolymer having alow molecular weight (hereinafter abbreviated as “HTR3”)

[0228] A linking style=4 type (ABAB type) block

[0229] [component A is a styrene block, and component B is a butadieneblock.]

[0230] A styrene content=29 wt %

[0231] A total amount of a vinyl content=32 wt %

[0232] A number average molecular weight=51,000

[0233] (3-6) An oil-containing 4 type hydrogenated styrene-butadienecopolymer having a high molecular weight (hereinafter abbreviated as“HTR4”)

[0234] A linking style=4 type (ABAB type) block

[0235] [component A is a styrene block, and component B is a butadieneblock.]

[0236] A styrene content=35 wt %

[0237] A total amount of a vinyl content=36 wt %

[0238] A number average molecular weight=120,000

[0239] A paraffin oil=a trade name PW-380 manufactured by Idemitsu KosanCo., Ltd.

[0240] A content of a paraffin oil=50 parts by weight based on 100 partsby weight of a hydrogenated styrene-butadiene copolymer

[0241] (4) A carbon type filler for an electrically conductive use(hereinafter abbreviated as “KB”)

[0242] A carbon black for an electrically conductive use [a trade name:Ketjen Black EC-600JD]

[0243] An amount of absorbing DBP=495 ml/100 g

[0244] A BET surface area=1,270 m²/g

[0245] (5) A carbon type filler for a non-electrically conductive use(hereinafter abbreviated as “CB”)

[0246] A carbon black for a coloring use [a trade name: MitsubishiCarbon Black RCF #45]

[0247] An amount of absorbing DBP=53 ml/100 g

[0248] A BET surface area=115 m²/g

[0249] (6) A styrene type thermoplastic resin (hereinafter abbreviatedas “PS”)

[0250] A homopolystyrene

[0251] A molecular weight=250,000

[0252] (7) A compatibilizer (hereinafter abbreviated as “MAH”)

[0253] A maleic anhydride [manufactured by Nippon Yushi K. K.]

Preparation Example 1

[0254] Preparation of EOR—15% MB

[0255] A temperature of a cylinder of a biaxial extruder [ZSK-25:manufactured by Werner & Pfleiderer Co. (Germany)] which has one feedopening at the upstream side and another feed opening at the centralpart thereof, was set at 220° C. From the feed opening at the upstreamside (hereinafter abbreviated as “Top-F”), EOR was supplied at aconstant rate of 8.5 kg/h, and from the feed opening at the central partthereof (hereinafter abbreviated as “Side-F”), KB was supplied at aconstant rate of 1.5 kg/h, and they were melted and kneaded topelletize.

[0256] A number of revolutions of the screw was 300 revolutions/min. Toremove volatile components, a vent for vacuum was provided at a positionbetween the Side-F and a die, and suction applied to the vent.

[0257] A master pellet (a concentration containing KB of 15 wt %) asobtained herein, is abbreviated as EOR-15% MB.

Preparation Example 2

[0258] Preparation of PA66—10% MB

[0259] Using the same extruder as in Preparation Example 1, acylindrical temperature thereof was set at 280° C. From the Top-F, PA66was supplied at a constant rate of 10 kg/h, and from the Side-F, KB wassupplied at a constant rate of 1.11 kg/h, and they were melted andkneaded to pelletize.

[0260] A number of revolutions of the screw was 320 revolutions/min. Toremove a volatile component, a vent for vacuum was provided at aposition between the Side-F and a die, and suction to a vacuum wasconducted.

[0261] A master pellet (a concentration containing KB of 10 wt %) asobtained herein, is abbreviated as PA66-10% MB.

Preparation Example 3

[0262] Preparation of PA66L—10% MB

[0263] The same procedure as Preparation Example 2 was conducted exceptthat PA66 was changed to PA66L, to obtain a master pellet.

[0264] A master pellet (a concentration containing KB of 10 wt %) asobtained herein, is abbreviated as PA66L—10% MB.

Preparation Example 4

[0265] Preparation of HTR2—10% MB

[0266] The same procedure as Preparation Example 1 was conducted exceptthat EOR was changed to HTR2, and from the Top-F, HTR2 was supplied at aconstant rate of 9 kg/h, and from the Side-F, KB was supplied at aconstant rate of 1 kg/h, to obtain a master pellet.

[0267] A master pellet (a concentration containing KB of 10 wt %) asobtained herein, is abbreviated as HTR2—10% MB.

Preparation Example 5

[0268] Preparation of HTR2—17% MB

[0269] The same procedure as Preparation Example 4 was conducted exceptthat from the Top-F, HTR2 was supplied at a constant rate of 8.3 kg/h,and from the Side-F, KB was supplied at a constant rate of 1.7 kg/h, toobtain a master pellet.

[0270] A master pellet (a concentration containing KB of 17 wt %) asobtained herein, is abbreviated as HTR2—17% MB.

Preparation Example 6

[0271] Preparation of HTR3—10% MB

[0272] The same procedure as Preparation Example 4 was conducted exceptthat HTR2 was changed to HTR3, to obtain a master pellet.

[0273] A master pellet (a concentration containing KB of 10 wt %) asobtained herein, is abbreviated as HTR3—10% MB.

Preparation Example 7

[0274] Preparation of HTR4—10% MB

[0275] The same procedure as Preparation Example 4 was conducted exceptthat HTR2 was changed to HTR4, to obtain a master pellet.

[0276] A master pellet (a concentration containing KB of 10 wt %) asobtained herein, is abbreviated as HTR4—10% MB.

Preparation Example 8

[0277] Preparation of KI—MB

[0278] To a biaxial extruder [PCM-30: manufactured by Ikegai Tekko Co.]of which a cylindrical temperature was set at 280° C., and which has onefeed opening at the upstream side, PA66L at a constant rate of 9.6 kg/h,and a powder-like potassium iodide (hereinafter abbreviated as “KI”) ata constant rate of 0.4 kg/h, were supplied respectively from separatefeeders, and they were melted and kneaded to pelletize.

[0279] A master pellet (a concentration containing KI of 4 wt %) asobtained herein, is abbreviated as KI—MB.

Preparation Example 9

[0280] Preparation of MPPE

[0281] A blend was obtained by dry blending 2 parts by weight of MAH and0.3 parts by weight of a radical initiator [Perhexa 25B: manufactured byNOF CORPORATION] with 100 parts by weight of PPE, and it was supplied toa biaxial extruder [PCM-30: manufactured by Ikegai Tekko Co.] of which acylindrical temperature was set at 320° C., and which has one feedopening at the upstream side, and they were melted and kneaded, topelletize.

[0282] Next, taking 1 g of the pellets obtained, putting them betweenwhat has been obtained by superposing a polytetrafluoroethylene sheet,an aluminum sheet, and an iron plate in this order from the inner side,by using a press molding machine set at a temperature of 280° C., acompression molding was conducted at a pressure of 100 kg/cm² to obtaina film.

[0283] A measurement of an infrared scpectrophotometric analysisconcerning the obtained film was conducted with a Fourier transforminfrared spectrophotometer of FT/IR-420 type manufactured by NipponBunko Co.

[0284] According to the measurement concerning the film, a peakoriginated from maleic acid added to the polyphenylene ether wasobserved at 1790 cm⁻¹.

[0285] The ratio of MAH added was 0.54 wt %, as calculated from theequation of a calibration curve preliminarily prepared by using amixture of PPE and MAH.

[0286] The MAH modified PPE as obtained herein is abbreviated as “MPPE”.

[0287] Next, each of measuring methods is explained in detail.

[0288] (Volume Inherent Resistance-1)

[0289] Both ends of a test piece for tensile test having a thickness of3.2 mm were cut with a precision cut-off saw to obtain a test piece of arectangular shape which possesses a length of 50 mm, and possesses a cutarea having a uniform sectional area (12.4×3.2 mm) at both ends. The cutareas at both ends of this test piece were coated with a silver paste,and were dried. After that, the value of resistance between the ends wasmeasured with a circuit tester, and volume inherent resistance wascalculated by using the equation (a). A value of the volume resistanceis represented as volume inherent resistance-1, and the value wasdescribed in Tables 1-4.

[0290] (Volume Inherent Resistance-2)

[0291] At the central parts of the surfaces facing each other of 50mm×2.5 mm of a molded piece of a plate shape which has a length of 90mm, a width of 50 mm, and a thickness of 2.5 mm, respectively, areas of30 mm×2.5 mm were coated with a silver paste, and were dried. Afterthat, the value of resistance between the ends was measured with acircuit tester. This was done five times with different plates, and anaverage value was calculated, and volume inherent resistance wascalculated by using the equation (a) as described below.

VR=R·w·t/l  (a)

[0292] wherein VR means volume inherent resistance (Ω·cm), R is theaverage value of an addition of resistance measured with a circuittester(Ω), w is the width of a part coated with a silver paste (cm), tis the height of a part coated with a silver paste (cm), l is thedistance between the areas which were coated with a silver paste (cm).

[0293] A value of the volume inherent resistance is represented asvolume resistance-2, and the value was described in Table 3.

[0294] (A Melt Flow Rate: MFR)

[0295] According to a method based on ISO 1133, it was conducted at 280°C., and at a load of 5 kg.

[0296] (A Coefficient of Linear Expansion)

[0297] A center part of a test piece for tensile test having a thicknessof 3.2 mm were cut with a precision cut-off saw to obtain a quadrangularpillar shape which has a thickness of 3.2 mm, a width of 5 mm, and alength of 10 mm. By using TMA-7 [manufactured by Perkin-Elmer Co.], acoefficient of linear expansion thereof was measured by raising atemperature thereof from 23° C. to 70° C. at a raising speed of 5°C./min, based on JIS K7197.

[0298] (An Izod Impact Test)

[0299] Izod impact strength notched of a test piece having a thicknessof 3.2 mm was measured based on ASTM D-256.

[0300] (A Dart Impact Test)

[0301] A dart impact test was conducted using a molded piece of a plateshape which has a length of 90 mm, a width of 50 mm, and a thickness of2.5 mm, by employing a graphic impact tester [manufactured by Toyo SeikiSeisaku-Sho Ltd.]

[0302] A testing method thereof is as follows. A test piece was clippedin a sample holder having a diameter of 40 mm, and a striker of aspherical shape (a weight thereof of 6.5 kg) having an apex diameter of13 mm was made to fall freely from the height of 100 cm above the testpiece, and the test piece was made to be broken. All of the energyrequired for the fracture thereon was measured, and was represented asall of the energy absorbed.

[0303] This test was carried out using 10 samples, and an average valueof an addition of the values measured concerning 8 pieces excluding amaximum one and a minimum one was regarded as all of the energy absorbedof the sample.

[0304] Furthermore, states of the fracture of test pieces which werebroken in the measurement, were observed and they were brieflyclassified as either a ductile fracture or a brittle fracture. Apercentage of ductility was calculated from the ratio of the number ofthe ductile fractures among the 10 test pieces.

A percentage of ductility=(a number of the ductile fracture/10)×100

[0305] (An Amount of Fines Caused by Pelletizing, which are Generatedwhen Processing of Extrusion is Conducted)

[0306] At a spinning nozzle, a water bath (a strand bath) and apelletizer were provided, and a drawing speed of the pelletizer wascontrolled so that a diameter of the strand having passed in the waterbath but before the pelletizer is in a range of 2 mm to 3 mm. Thereon, alength of the strand to be dipped in the water bath was made to be 100cm. In this connection, water temperature was 13° C.

[0307] Pellets from the pelletizer thereon were taken by about 100 g,and a precise weight thereof was measured. The value is taken as W1.

[0308] Next, the pellets from the pelletizer of which a precise weightwas measured, were spread on a woven metallic wire screen of 20 mesh,and were well shaken. After fractionating pellets and fines caused bypelletizing, a precise weight of the pellets remaining on the wovenmetallic wire was measured. The value is taken as W2.

[0309] The ratio of fines caused by pelletizing (W %) was calculatedfrom W1 and W2 of these, by using the following equation.

W %=(1−W2/W1)×100

[0310] (An Adhesion Property with Coats)

[0311] According to the method as described in JP-A-60-65035, a moldedpiece in the form of a plate which has a length of 90 mm, a width of 50mm, and a thickness of 2.5 mm, was coated with a thermosetting acrylicresin coating material diluted with an exclusively used thinner by usinga spray gun. It was left to stand at a room temperature for 30 min., andwas thermally cured at 150° C. for 30 min., and a coated material wasobtained. Next, a peeling test using a checkerboard having a division ofa square of 1 mm length concerning coats of the coated material wasconducted based on JIS K5400-1979, and a number of divisions which didnot peel off, among 100, was calculated.

Example 1

[0312] A cylindrical temperature of Top-F to Side-F of a biaxialextruder [ZSK-40: manufactured by Werner & Pfleidere Co. (Germany)]which has one feed opening at the upstream side and another feed openingat the central part thereof, was set at 320° C., and that of Side-F to adie was set at 280° C. From Top-F and Side-F, respectively, what are dryblended in a ratio as described in Example 1 of Table 1 were supplied,and they were melted and kneaded to pelletize. The amount of finescaused by pelletizing, which were generated when processing of extrusionwas conducted, was measured at the same time.

[0313] In this connection, a number of revolutions of the screw thereonwas 300 revolutions/min. To remove the volatile components, a vent forvacuum was provided at two positions, one just before the Side-F and onebetween the Side-F and the die, and suction was applied to the vent.

[0314] By using an injection molding machine [IS-80EPN: manufactured byToshiba Kikai Co. (Japan)] set at a cylindrical temperature of 290° C.and at a mold temperature of 80° C., the obtained pellets were molded toobtain a molded piece necessary for each of the measurements. Theresults were also described in Table 1.

[0315] Further, to confirm that KB, which is a carbon type filler for anelectrically conductive use, resides in a phase of PPE, a central partof a pellet obtained was cut with an ultra-microtome in a directionperpendicular to a flowing direction in the form of an ultra-thin slice(conditions of cutting: a temperature of cutting: −40° C., thickness ofthe slice: 70 nm), and the ultra-thin slice prepared was left to standfor 20 min. in an atmosphere of a vapor of ruthenium tetroxide, and isdyed. The dyed ultra-thin slice was taken at a magnification of about20,000 with a transmission electron microscope, and as a result, thepresence of carbon in a phase of PPE could be confirmed. The electronmicroscope photograph obtained was shown in FIG. 1, and a schematicdrawing thereof was shown in FIG. 2. (In the schematic drawing, a partencircled with a black line indicates a phase of a polyphenylene ether,and a black dot indicates KB.)

[0316] From these Figures, an appearance can be recognized wherein aphase of a polyphenylene ether showing a grey color resides in acontinuous phase of a polyamide, and in the phase of a polyphenyleneether, KB is interspersed in a state of particles.

Comparative Example 1

[0317] The same procedure as in Example 1 was conducted except that thecomposition formulated was changed to the ratio described in ComparativeExample 1 of Table 1. In this connection, the final composition of thepresent Comparative Example is quite the same composition as that ofExample 1.

[0318] Further, to confirm a location of KB, which is a carbon typefiller for an electrically conductive use residing, a photograph wastaken with a transmission electron microscope, as in Example 1. Theelectron microscope photograph obtained is shown in FIG. 3, and aschematic drawing thereof is shown in FIG. 4.

[0319] From FIGS. 3 and 4, the presence of KB in a phase of PPE couldnot be recognized. This is true because a phase of a polyphenylene ethershowing a grey color resided in a continuous phase of a polyamide, butalmost all of the KB was interspersed in the phase of a polyamide in theform of particles.

Examples 2 to 5 and Comparative Example 2

[0320] The same procedure as in Example 1 was conducted except that thecompositions formulated were changed to the ratios described in Table 1.In this connection, the final compositions of the inventive Examples andComparative Example are quite the same composition as those of Example 1and Comparative Example 1.

[0321] The results are described in Table 1 below the composition ofeach of the Examples and the Comparative Examples. TABLE 1 ExampleExample Example Example Example Comp. Comp. unit 1 2 3 4 5 Ex. 1 Ex. 2Top-F PPE-L wt part 30 30 30 30 30 30 30 MAH wt part 0.2 0.2 0.2 0.2 0.20.2 0.2 HTR2 wt part 17 17 17 17 KB wt part 3.5 2 HTR2-10% MB wt part 1919 HTR2-17% MB wt part 20.5 Side-F PA66L wt part 49.5 49.5 36 36 49.5 1949.5 KB wt part 1.5 3.5 PA66L-10% MB wt part 15 15 34 Total wt part100.2 100.2 100.2 100.2 100.2 100.2 100.2 Composition PE wt % 29.9 29.929.9 29.9 29.9 29.9 29.9 MAH wt % 0.2 0.2 0.2 0.2 0.2 0.2 0.2 HTR2 wt %17.0 17.0 17.1 17.0 17.1 17.0 17.0 PA66L wt % 49.4 49.4 49.4 49.4 49.449.5 49.4 KB wt % 3.5 3.5 3.4 3.5 3.4 3.4 3.5 Total wt % 100.0 100.0100.0 100.0 100.0 100.0 100.0 Presence of a carbon type filler yes yesyes yes yes no no for an electrically conductive use Volume inherentresistance-1 Ω · cm 10⁶⁻⁷ 10⁶⁻⁷ 10⁵⁻⁶ 10⁵⁻⁶ 10⁵⁻⁶ 10⁵⁻⁶ 10⁵⁻⁶ Fluidity(MFR) 280° C., 5 kg load g/10 min 57 50 36 32 27 23 18 Coefficient oflinear expansion × 10⁻⁵° C.⁻¹ 7.7 8.0 8.5 7.4 7.8 10.7 9.9 23° C.-70° C.Izod impact strength 23° C. J/m 186 178 158 130 138 157 143 Amount offines generated wt % 0.1 0.1 0.1 0.13 0.19 1.19 0.88 or less or less orless

[0322] It has been proved that even though final compositions are quitethe same, physical properties thereof are greatly differentiateddepending upon whether or not KB resides in a phase of PPE.

Examples 6 to 10 and Comparative Examples 3 to 4

[0323] The same procedure as in Example 1 was conducted except that thecompositions formulated were changed to the ratios described in Table 2.In this connection, the results are described in Table 2 below thecomposition of each of the Examples and the Comparative Examples. TABLE2 Example Example Example Example Example Comp. Comp. unit 6 7 8 9 10Ex. 3 Ex. 4 Top-F PPE-L wt part 30 30 30 26 20 30 MPPE wt part 30 MAH wtpart 0.2 0.2 0.2 0.2 0.2 0.2 PS wt part 4 10 HTR2 wt part 17 17 17 17 CBwt part 3.5 KB wt part 3.5 3.5 HTR2-10% MB wt part 19 19 HTR3-10% MB wtpart 19 Side-F PA66L wt part 49.5 36 36 36 50 50 50 KB wt part 0.3PA66L-10% MB wt part 15 15 15 Total wt part 100.2 100.2 100.2 100 100.7100.7 97.5 Composition PPE-L wt % 29.9 29.9 29.9 25.8 19.9 30.8 MPPE wt% 30.0 MAH wt % 0.2 0.2 0.2 0.2 0.2 0.2 PS wt % 4.0 9.9 HTR2 wt % 17.017.1 17.1 16.9 16.9 17.4 HTR3 wt % 17.1 PA66L wt % 49.4 49.4 49.4 49.549.7 49.7 51.3 CB wt % 3.5 KB wt % 3.5 3.4 3.4 3.4 3.5 Total wt % 100.0100.0 100.0 100.0 100.0 100.0 99.7 Presence of a carbon type filler yesyes yes yes yes no no for an electrically conductive use Volume inherentresistance-1 Ω · cm 10⁶⁻⁷ 10⁵⁻⁶ 10⁵⁻⁶ 10⁵⁻⁶ 10⁶⁻⁷ ∞ ∞ Fluidity (MFR)280° C., 5 kg load g/10 min 50 36 43 33 55 85 125 Coefficient of linearexpansion × 10⁻⁵° C.⁻¹ 8.0 8.5 8.2 7.9 9.0 10.3 11.3 23° C.-70° C. Izodimpact strength 23° C. J/m 178 158 191 160 144 105 191 Amount of finesgenerated wt % 0.1 0.1 0.1 0.15 0.23 0.52 0.1 or less or less or less orless

[0324] It has been proved that when an amount used of a carbon typefiller for an electrically conductive use is extremely small, or acarbon black for a coloring use is used instead of a carbon type fillerfor an electrically conductive use, a balance of physical properties isworsened.

Examples 11 to 13 and Comparative Examples 5 to 7

[0325] The same procedure as in Example 1 was conducted except that thecompositions formulated were changed to the ratios described in Table 3.In Examples 11 to 13 and Comparative Examples 5 to 7, in addition to thevalves given in Example 1, valves for volume inherent resistance-2 and adart impact test are also given.

[0326] In this connection, the results are described under the headingsin Table 3 for each of the inventive Examples and Comparative Examples.

[0327] As compared with volume inherent resistance-2, some scattering isobserved in volume inherent resistance-1, but a large difference cannotbe recognized between the two as a value of volume inherent resistance.This is believed to be because resistance is substantially measuredbetween the cut surfaces, since at one end of a molded piece in the formof a plate, there is a gate of a film shape, and the portion is cut.TABLE 3 Example Example Example Comp. Comp. Comp. unit 11 12 13 Ex. 5Ex. 6 Ex. 7 Top-F PPE-H wt part 30 30 30 30 30 30 MAH wt part 0.3 0.30.3 0.3 0.3 0.3 HTR1 wt part 10 10 10 10 10 10 Side-F PA66 wt part 45 4522.5 24 32 2 PA6 wt part 22.5 22.5 EOR wt part 5 13 13.5 12.5 MEOR wtpart 2 2 2 2 2 2 PA66-10% MB wt part 23 15 23 EOR-15% MB wt part 15 1015 Total wt part 102.3 102.3 102.3 102.3 102.8 102.3 Composition PPE-Hwt % 29.3 29.3 29.3 29.3 29.2 29.3 MAH wt % 0.3 0.3 0.3 0.3 0.3 0.3 HTR1wt % 9.8 9.8 9.8 9.8 9.7 9.8 PA66 wt % 44.0 44.0 22.0 43.7 44.3 22.2 PA6wt % 22.0 22.0 EOR wt % 12.5 13.2 12.5 12.7 13.1 12.2 MEOR wt % 2.0 2.02.0 2.0 1.9 2.0 KB wt % 2.2 1.5 2.2 2.2 1.5 2.2 Total wt % 100.0 100.0100.0 100.0 100.0 100.0 Presence of a carbon type filler yes yes yes nono no for an electrically conductive use Volume inherent resistance-1 Ω· cm 10⁴⁻⁵ 10⁵⁻⁶ 10⁴⁻⁵ 10⁴⁻⁵ 10⁵⁻⁶ 10⁴⁻⁵ Volume inherent resistance-2 Ω· cm 4.2 × 10⁴ 3.2 × 10⁵ 2.0 × 10⁴ 5.8 × 10⁴ 7.8 × 10⁵ 2.5 × 10⁴Fluidity (MFR) 280° C., 5 kg load g/10 min 27 32 28 12 17 10 Coefficientof linear expansion × 10⁻⁵° C.⁻¹ 9.0 8.9 9.2 10.2 10.5 10.3 23° C.-70°C. Izod impact strength 23° C. J/m 205 210 220 135 142 128 Dart impacttest Al energy absorbed J 39.8 47.2 53.4 28.4 32.3 30.0 Percentage ofductility % 100 100 100 0 20 10 Amount of fines generated wt % 0.18 0.160.16 0.66 0.51 1.09

[0328] Comparative Examples respectively corresponding to inventiveExamples 11, 12, and 13 are Comparative Examples 5, 6, and 7. It hasbeen proved that physical properties are greatly different dependingupon whether or not a carbon type filler for an electrically conductiveuse resides in a phase of PPE.

Examples 14 and 15

[0329] The same procedure as in Example 1 was conducted except that thecompositions formulated were changed to the ratios described in Table 4.In Examples 14 and 15, in addition to the measuring valves in Examples1, the valve of an adhesion property with coats was also determined.

[0330] In this connection, the results are described under the headingsin Table 4 for each of the inventive Examples and Comparative Examples.TABLE 4 Exam- Exam- Exam- unit ple 3 ple 14 ple 15 Top-F PPE-L wt part30 30 30 MAH wt part 0.2 0.2 0.2 HTR2 - 10% MB wt part 19 HTR4 - 10% MBwt part 19 19 Side-F PA66L wt part 36 36 31 KI-MB wt part 5 PA66L - 10%MB wt part 15 15 15 Total wt part 100.2 100.2 100.2 Composition PPE-L wt% 29.9 29.9 29.9 MAH wt % 0.2 0.2 0.2 HTR2 wt % 17.1 HTR4 wt % 17.1 17.1PA66L wt % 49.4 49.4 49.2 KI wt % 0.2 KB wt % 3.4 3.4 3.4 Total wt %100.0 100.0 100.0 Presence of a carbon type yes yes yes filler for anelectrically conductive use Volume inherent resistance-1 Ω · cm 10⁵⁻⁶10⁵⁻⁶ 10⁵⁻⁶ Fluidity (MFR) 280° C., g/10 min 36 40 39 5 kg loadCoefficient of linear × 10⁻⁵° C.⁻¹ 8.5 7.5 7.6 expansion 23° C.-70° C.Izod impact strength 23° C. J/m 158 180 175 Amount of fines generated wt% 0.1 0.1 0.13 or less or less Adhesion property with coats number/100 —53 100

[0331] It has been proved that by changing an impact modifier from anABA type to an ABAB type, a balance of a coefficient of linear expansionand an impact resistance is further greatly improved, and by adding KI,an adhesion property with coats also is enormously improved.

INDUSTRIAL APPLICABILITY

[0332] The resin composition of the present invention is a resincomposition which has excellent electrical conductivity, fluidity, andan excellent balance of a coefficient of linear expansion and an impactresistance, and wherein generation of fines caused by pelletizing can belargely suppressed when processing of extrusion thereof is conducted.

1. A resin composition comprising a polyamide, a polyphenylene ether, animpact modifier, and a carbon type filler for an electrically conductiveuse, wherein the filler resides in a phase of the polyphenylene ether.2. The resin composition according to claim 1, wherein the amount of thecarbon type filler for an electrically conductive use is 0.5 to 50 partsby weight based on 100 parts by weight of a mixture consisting of 40 to90 parts by weight of a polyamide, 5 to 50 parts by weight of apolyphenylene ether, and 5 to 30 parts by weight of an impact modifier.3. The resin composition according to claim 1 or 2, which does notcontain a styrene type thermoplastic resin in an amount of at least 5parts by weight based on 100 parts by weight of the total amount of apolyamide and a polyphenylene ether.
 4. The resin composition accordingto any one of claims 1 to 3, wherein the impact modifier is at least oneselected from the group consisting of a block copolymer of an aromaticvinyl compound and a conjugated diene compound, a hydrogenated productthereof, and an ethylene-α-olefin copolymer, wherein the block copolymerof an aromatic vinyl compound and a conjugated diene compound comprisesa polymer block segment (A) mainly composed of an aromatic vinylcompound and a polymer block segment (B) mainly composed of a conjugateddiene compound, and a linking structure of the polymer block segments isat least one selected from the group consisting of an AB type, an ABAtype, and an ABAB type.
 5. The resin composition according to any one ofclaims 1 to 4, wherein the impact modifier is a block copolymer of anaromatic vinyl compound and a conjugated diene compound of an ABAB type,which comprises a polymer block segment (A) mainly composed of anaromatic vinyl compound and a polymer block segment (B) mainly composedof a conjugated diene compound, and/or a hydrogenated product thereof.6. The resin composition according to claim 4, wherein a content ofethylene unit in the ethylene-α-olefin copolymer is 30 to 95% by weightbased on the total amount of the ethylene-α-olefin copolymer.
 7. Thecomposition according to claim 4 or 6, wherein the ethylene-α-olefincopolymer is an ethylene-α-olefin copolymer produced with a single-sitecatalyst.
 8. The resin composition according to any one of claims 1 to7, wherein the impact modifier is an impact modifier preliminarily mixedwith an oil containing a paraffin mainly, and the amount of the oil isnot greater than 70 parts by weight based on 100 parts by weight of theimpact modifier.
 9. The resin composition according to any one of claims1 to 8, wherein the carbon type filler for an electrically conductiveuse is at least one selected from the group consisting of a carbonblack, a nanotube carbon, a carbon fiber, and graphite, for anelectrically conductive use.
 10. The resin composition according to anyone of claims 1 to 9, wherein the carbon type filler for an electricallyconductive use is a carbon black for an electrically conductive use. 11.The resin composition according to any one of claims 1 to 10, whichcomprises less than 2 parts by weight of a metallic salt as representedby the following formula, based on 100 parts by weight of the totalamount of a polyamide, a polyphenylene ether, an impact modifier, and acarbon type filler for an electrically conductive use, M^(y+) _(n)X^(z−)_(n·y/z) wherein M^(y+) represents at least one metallic ion selectedfrom the group consisting of copper, nickel, tin, cerium, and analkaline metal, and X^(z−) represents at least one negatively chargedion selected from the group consisting of a halide ion and a carboxylateion, n is an integer of 1 to 6, y is an integer indicating electriccharge of a positive ion of M, and z is an integer indicating electriccharge of a negative ion of X.
 12. The resin composition according toclaim 11, wherein the metallic salt is a metallic salt comprising analkaline metallic ion and an iodic ion.
 13. The resin compositionaccording to claim 11 or 12, wherein the metallic salt has beenpreliminarily mixed with a part or the whole of a polyamide.
 14. Theresin composition according to any one of claims 1 to 13, wherein a partor the whole of a polyphenylene ether is a modified polyphenylene etherwhich has in the molecular structure thereof at least one C—C doublebond or triple bond, and has at least one of a carboxylic acid group, anacid anhydride group, an amino group, a hydroxyl group, or a glycidylgroup.
 15. The resin composition according to any one of claims 1 to 14,wherein the carbon type filler for an electrically conductive use hasbeen preliminarily melted and kneaded with an impact modifier.
 16. Theresin composition according to any one of claims 1 to 14, wherein thecarbon type filler for an electrically conductive use has beenpreliminarily melted and kneaded with the impact modifier, and thenadded in the form of a master batch.
 17. The resin composition accordingto any one of claims 1 to 14, wherein the carbon type filler for anelectrically conductive use has been preliminarily melted and kneadedwith a mixture containing an impact modifier and a polyphenylene ether.18. The resin composition according to any one of claims 15 to 17,wherein the ratio of a carbon type filler for an electrically conductiveuse and an impact modifier which are preliminarily melted and kneaded,is 5 to 30 parts by weight of a carbon type filler for an electricallyconductive use based on 100 parts by weight of an impact modifier. 19.The resin composition according to any one of claims 15 to 18, whereinthe amount of a carbon type filler for an electrically conductive usewhich is preliminarily melted and kneaded, is not less than 50% byweight based on the whole amount used of a carbon type filler for anelectrically conductive use.
 20. The resin composition according to anyone of claims 1 to 19, wherein a morphology of dispersion where theimpact modifier is included in a phase of a polyphenylene ether isformed, and not more than the largest half of the whole of a carbon typefiller for an electrically conductive use which resides in the phase ofa polyphenylene ether, is contained in the impact modifier.
 21. Aprocess for producing the resin composition according to claim 1,wherein a carbon type filler for an electrically conductive use ispreliminarily melted and kneaded with an impact modifier.
 22. Theprocess for production according to claim 21, wherein the carbon typefiller for an electrically conductive use is preliminarily melted andkneaded with an impact modifier, and then added as a form of a masterbatch.
 23. The process for production according to claim 21 or 22,wherein the ratio of a carbon type filler for an electrically conductiveuse and an impact modifier which are preliminarily melted and kneaded,is 5 to 30 parts by weight of the carbon type filler for an electricallyconductive use based on 100 parts by weight of the impact modifier. 24.The process for production according to any one of claims 21 to 23,wherein the amount of a carbon type filler for an electricallyconductive use which is preliminarily melted and kneaded, is not lessthan 50% by weight based on the whole amount used of the carbon typefiller for an electrically conductive use.